Production of hydrocarbons



y 1942- T. B. PRICKETT 2,289,329

PRODUCTION OF HYDRQCARBONS Filed July 16, 1938 .2 Sheets-Sheet 2 t 9/REACTION ZONE H a. l2 SEPARATOR PURGING ZONE INVENTOR' THuMAs B.PRICKETTATTORNEY Patented July 7, 1942 UNITED STATES PATENT OFFICE- PRODUCTIONOF I- IYDROCARBONS Thomas B. Priekett, Woodbury, N. 1., assignor toHoudry Process Corporation, Wilmington, DeL, a corporation of DelawareApplication July 16, 1938, Serial No. 219,537

12 Claims.

The present invention relates to the production of valuable hydrocarbonsfrom starting material comprising or containing bitumens having originin petroleum, coal, shale, schist and the like, or from vaporous orgaseous materials capable of reacting to yield hydrocarbon products.More particularly, it is concerned with processes for effectingsynthesis, decomposition, purification and other reactions in thepresence of absorbent and/or adsorbent contact material capable ofpromoting; entering into, or in any way assisting the desired reactions.It is particularly directed toward systems wherein reactants and solidcontact material flow simultaneously through a reaction zone.

One object of the present invention is to improve systems of the abovedescribed type wherein the desired reactions are effected in vaporphase. Another object is toeffect close control over reaction conditionsin such systems. Another object is to devise an improved closed circuitwherein the contact mass is flowed through the reaction zone andthereafter reactivated and returned to the reaction zone. Another objectis to maintain the solid contact material in dry or substantially dryform at all times. Another object is to utilize process fluids to assistin handling oi the contact mass and/or in conditioning of the same.Other objects will be apparent from the detailed description whichfollows.

Concrete embodiments of the invention are disclosed in the accompanyingdrawings in which:

Fig. l is a diagrammatic flow chart illustrating a closed circuit of theabove described type and one use of a proces fluid to assist inconditioning of the contact mass;

Fig. 2 is a modified flow chart illustrating another use of processfluids to assist in the treatment of the contact material;

Fig. 3 is another modified flow chart showing still difi'erentutilization of process fluids in handling the contact material;

Figs. 4, and 6 are somewhat diagrammatic sectional views of highlyadvantageous types of separating equipment for use in the circuits shownin Figs. 1, 2 and 3, Fig. 4 being a sectional elevation of one type ofseparator, Fig. 5 a sectional elevation of a modified form of separatorand Fig. 6 a sectional plan view taken substantially on line 6-6 of Fig.5;

And Fig. 7 is a sectional elevation of one type of impelling means forcontact solid.

Referring to the drawings, and particularly to Figs. 1, 2 and 3,reactants capable of entering into the desired reaction and comprising,for example, distillate or residual higher boiling hydrocarbons capableof transformation into lower boiling products including gasoline andgas, or ordinarily gaseous hydrocarbons capable of being cracked orpolymerized to yield higher boiling liquids, or hydrocarbon distillatescontaining corrosive or other impurities, may be forced into and throughheater H to be heated to reaction temperature and then passed in vaporphase, and often in superheated condition, through lines 8 and II intoreaction vessel or zone 9. Before admission to the latter the reactantsare mixed with a suitably controlled quantity of desired solid contactmaterial in heated condition supplied, for example, to line H from feedhopper or bin ID, in any known or desired manner, as for example, bymeans of a screw conveyor or other suitable impelling means.

The temperature of the contact mass at the instant of its presentationto the reactant vapors is preferably at or at least near the temperatureof the latter, thus providing many important process advantages whichreflect in improved control over the course and extent of the reactions.In some instances, as when the desired reaction is endothermic and/orwhen the reaction tends to proceed to completion in heater H to yieldinferior products, the contact mass may be at somewhat highertemperature than the reactants. Such control of the temperatures of bothreactants and contact mass minimizes or even avoids undesirablereactions leading, in many hydrocarbon processes, to formation of excessquantities of coke and light gases caused by overheating of the chargeprior to its introduction into the reaction zone. It also avoidsundesirable reactions and loss of activity occasioned by condensation ofportions of the reactant vapors on or in the contact material.

After flowing the entire or substantially the entire length of reactionzone 9 the mixture of vapors and contact material discharges throughline l2.into separator I 3 in which the dry solid settles and iswithdrawn by line H. The latter preferably leads to a zone forreactivatin'g or revivifying the contact mass. Meanwhile, vaporousreaction products are conducted by line l5 to a suitable finishing orother treatment, the nature of which depends upon the character of thereaction products, and may comprise rectification, for example, in afractionator such as 43 (Fig. 1) discharging distillate and residualfractions by lines 44 and 45. Such distillate fraction may. if desired,be condensed in cooler 46 and conducted by line 41 to any furtherdesired or required treatment. Any mall quantity of finely dividedcontact material which may leave separator I3 by line I5 may berecovered from the residual fraction in line 45 as by filtration or thelike.

The reaction chamber or space in the vessel comprising reaction zone 9is so designed and disposed that settling and accumulation of solidtherein is avoided, due consideration being taken of the velocity offlow therethrough and of the density, size and other characteristics ofthe contact mass. Although satisfactory results may be obtained by highvelocity flow, through a horizontal chamber, of vapors carrying finelydivided or powdered contact mass in suspension, the reaction chamber ispreferably disposed in inclined or vertical position thereby to permitfree or substantially free fall of contact mass from the inlet to outletof the same, whether the mass be in powdered, granulated, fragmentary ormolded form.

According to a preferred aspect of the invention, centrifugal action isutilized to effect separation of vaporous reaction products and drycontaminated contact solid in separator I3. One simple way of inducingsuch centrifugal action is to admit the mixture of solid and vapor tothe separation chamber tangentially and at high velocity to providerapid rotary or whirling motion therein, as indicated for example inFigs. 4, 5 and 6. In Fig. 4, the stream of solid and fluid entersenlarged chamber C of separator I3a through substantially tangentiallydisposed inlet line In, preferably having its discharge opening abovethe lower end of vapor line I5a, separated solid material settling tothe bottom of chamber C and being withdrawn by line Ila.v When thecontact mass leaving reaction zone 9 is in very fine state of division,part of it sometimes remains in suspension even under the low velocityvertical flow conditions obtaining in the lower portions of the chamberand tends to be carried into conduit Ia. In such cases, it is desirableto mechanically induce centrifugal action in substitution for or tosupplement the effect of the tangential flow in chamber C. One method ofutilizing supplementary separation is illustrated in Figs. 5 and 6.

In these figures, separator I3b contains a lower chamber CI providedwith inner annular shell I 30 and fed by tangentially disposed line I2b.This lower chamber discharges vapor, with possibly some finely dividedsolid held in suspension therein, through line I51) and into a secondand upper separating chamber or zone C2 containing fan blades B or thelike rotated at high speed, as by motor M. The finely divided solidseparated by mechanically induced centrifugal action in chamber C2 fallsdown annular chamber C3 to combine with the somewhat larger materialseparated in chamber CI prior to withdrawal by line I 4b. Simultaneouslyvapors flow to the desired treating or processing equipment by line I50.

The dry, hot contact material in line I4, prior to reintroduction intoreaction zone 9, has adherent fluid and/or solid reaction productsremoved from it. Since the used contact mass usually contains valuableadsorbed fiuid reaction products, it is preferable to remove suchproducts by a purging operation utilizing vacuum and/or a purgingmedium, for example, a suitable inert fluid such as flue gases or steam.This purging operation may be conducted in a single container, such asI6, through which the contact mass is allowed to flow slowly. It ispreferable, however,

to utilize a plurality of purging containers I6 arranged and adaptedalternately to receive contact material from line I4 as through valvedbranches I1 and to discharge the purged contact mass, as for example,into line I8 by valved branches 20. When a plurality of purging chambersare used, each may be sealed from the rest of the system, thus providingfor use of any desired purging method without interrupting or in any wayinterfering with the operating conditions in the rest of the plant. Iffurther regeneration of the contact mass is necessary, as for example toremove coky, pitchy, sulphurous or other burnable deposits, the purgedmaterial, substantially free of volatile products, may be conducted byline I8 into regenerating zone I9, which may comprise or contain anyknown or desired type of equipment for removing combustible depositsfrom contact masses. This equipment may be a rotary kiln or a single ormultiple hearth burner, as for example, a multiple hearth burnerprovided with cooled rabble arms, as commonly used for burning clays andother contact masses. When the contact mass is in the form ofcomparatively large pieces of uniform or substantially uniform size andshape it may advantageously be regenerated in a reaction zone providedwith one or more series of perforated inlet and/or outlet members forregenerating medium and/or products embedded in the mass as disclosedfor example in United States Patents 1,987,904 and 2,042,468, issued toEugene J Houdry, January 15, 1935, and June 2, 1936, respectively. Theburned or regen erated contact material issuing from regenerating zoneI9, as by line 2I, is then returned, while still hot and at controlledtemperature to feed bin or hopper In. Any known or desired conveyingmeans, including bucket elevators or pneumatic conveyors may be utilizedfor this purpose.

In certain of its aspects, the invention involves utilizing processfluids to assist in conditioning the used and contaminated contactmaterial for further treatment or use, or in presenting the contact massin active form to the reaction zone. One economically advantageous useof a process fluid is indicated in Fig. 1, in which all or any desiredportion of the regeneration fumes issuing from regenerating zone I9 byline 22 may be utilized to regulate the temperature of fresh orregenerated contact material entering or about to 1 enter reaction zone9. To this end, regeneration fumes at suitable temperature, regulated inany known or desired manner, as for example by admission thereto of aheating or cooling fluid, such as steam or air, as by line 25, may bepassed in heat exchange relation with the contact mass in feed hopperI0, as through a jacket such as 23 or through a coil or other suitableheat exchange device contained within or otherwise associated withhopper ID. The regeneration fumes may then be discharged by line 24.

One of the process fluids, and particularly regeneration fumes, may'findvaluable use in removing reaction products from used contact materialpreparatory to further reactivation or regeneration. As shown in Fig. 2,any desired portion of the regeneration fumes in line 22 may beconducted by line 26 to all or any desired one or group of the purgingcontainers I6 as through valved branches 21. The hot fumes coming intocontact with the contaminated solid in the purging zone, in addition toeffecting removal of fluid adsorbed therein, assist in adjusting thetemperature of the contact mass to the level suitable for regeneration.The hot fumes loaded with purged hydrocarbon fluid issuing from thepurging zone by valved branches 28 leading to line 48 maybe cooled in asuitable cooler 29 to effect condensation of valuable hydrocarbons. Thelatter may then be separated in any known manner as in a conventionalvaporliquid separator, such as indicated at 30. If desired or necessary,the composition of the regeneration fumes may be modifled prior to theiruse as purging fluid to insure against combustion in the purging zone.To this end, the fumes may be diluted with a suitable inert fluid, suchas steam, supplied by line 4i. Or, bumable components such as carbonmonoxide and hydrocarbon vapors may be removed along with oxygen by asuitable catalytic combustion process, for ex ample, one employing acopper catalyst. One

suitable process is disclosed in the copending application of Eugene J.Houdry, Serial No. 78,542, filed May 8, 1936, replaced by substituteapplication Serial No. 266,010, filed April 4, 1939, which issued asPatent No. 2,248,994 on July 15, 1941.

Simplicity and economy of operation are realized when process fluids,including reactants and regeneration fumes, are utilized to.pneumatically convey the contact solid from the regenerating zone to thereaction zone. When comparatively large quantities of contact materialare desired or required for the reaction, as is the case in someprocesses for transforming higher boiling starting material into lowerboiling or distillate products, regeneration fumes may advantageous- 1ybe utilized for this purpose. As illustrated in Fig. 3, regeneratedcontact material discharged by line 2| from regenerating zone l9 may becollected in feed hopper 3|. Thence it may flow by gravity through line32 to be picked up in any suitable type of impelling means, indicated atD, by regeneration fumes forced through line 22 by compressor or blower33, the fumes and suspended solid then passing through' line 34 to feedbin or hopper l0. One simple form of impelling means for combining theselected process fluid with the contact mass is somewhatdiagrammatically illustrated in Fig. '7, in which the desired quantityof conveying fluid in line 22 is injected at high velocity throughnozzle 22ainto chamber K. The jetted fluid then picks up the contactsolid M admitted to chamber K by. conduit 32 and impels the same intoand through conduit 34.

When desired or required, the temperature of either or both the contactmass and regeneration fumes may be regulated-by means of suitable heatexchangers, located in either or both lines32 and 22 respectively, asfor example, cooler 36 in line 22 provided'with a by-pass therearound(Fig. 3). When the quantity of regeneration fumes is insufficient toconvey the total desired amount of contact material it may be augmentedby controlled quantities of a suitable fluid, preferably of inertnature, supplied by valved line 31 from any desired source; Whenregeneration fumes or other diluent fluid is utilized as conveyingmedium, feed hopper i preferably assumes a form (Fig. 3) capable ofseparating vapors from solid and provided with a gas outlet 38. Hopperl0 may then be, for example, a centrifugal separator of the typeutilized for separa or l3. Insome processes it is desirable hopper andseparator l0 as through valved bypass 39. If regeneration fumes intendedfor use as a conveying fluid contain undesirable components, such asfree oxygen, carbon monoxide or "tmaterial are needed for the desiredreaction, as

for example, for refining comparatively sweet quired heat exchanger.such as heater or cooler 49, for the regenerated contact material may belocated in line ll before its junction with line 8. The heated reactantvapors in line 8 may then pick up the contact solid in any desired typeof pneumatic impeller D and convey the solid through line H to reactionzone 9, proper compensation due to time in the former being made for thecontact time in the latter.

With some hydrocarbon reactions, as may be illustrated by certainpolymerization processes, the contact material acquires only smallamounts of contaminating deposit and may be advantageously andeconomically reused after being purged of adsorbed fluid reactionproducts and.

the purging containers It may be supplemented or replaced by vacuum,utilized, for example,

i the desired reactions.

to include another process fluid, for example, a I

diluting or carrying agent, in the charge to the reaction zone. In suchcases, anydesired por tion of the mixture of solid and flue gas, steamor other conveying fluid may short-circuit feed after the mannerdisclosed and claimed in United States Patent 2,095,265, issued October12, 1937, to J. H. Pew, or in United States Patent 2,095,264, issuedOctober 12, 1937, to A. E. Pew, Jr. Such vacuum may be derived from anysuitable source, as from a steam evacuating jet such as 42 (Fig. 1)located in line 48.

The invention, in its broad aspects, is not limited to the use of anyparticular contact mass but embraces utilization of any known or desiredcontact solid capable of promoting or assisting The mass may, forexample, be of silicious and/or aluminous nature and of natural orartificial origin, or it may comprise any' metal or oxide, alone,admixed with, incorporated within or otherwise associated with a supportof silicious or other nature. In-one of the more common applications ofthe invention a silicious adsorbent contact mass, for example, asynthetic blend of silica and alumina or an active or activatedhydrosilicate of alumina may be utilized to promote transformation ofhigher boiling distillate or residual hydrocarbons into the higherboiling vapors, heated to about 850 F'., for example, may be mixed withthe adsorptive mass in the form of powdered or fragmentary particles ofa size not in excess of about 8 mesh and supplied at a temperaturewithin the range of 800 to 900 F. After flowing through the reactionzone and being separated from the vaporous reaction products bycentrifugal action in a separator of the type disclosed, for example, inFig. 4,- the dry, hot contact mass is preferably purged of adsorbed andabsorbed vapors and regenerated by combustion at controlled temperaturenot in excess of 1150 to 1200 F. and preferably of the order of 1000 F.before being re-introduced at adjusted temperature into the stream ofreactant vapors.

It is apparent from the above that the invention provides for control ofreaction conditions in a manner to minimize side or other undesiredreactions caused by overheating or condensation of reactants prior to orduring the desired contact operation. Important advantages are realizedby maintaining the contact mass in hot, dry condition during all phasesof its handling or treatment. These advantages may be augmented byeconomical use of process fluid to assist in treatment or handling ofthe contact solid in one or more steps of the operation.

I claim as my invention:

1. In effecting hydrocarbon reactions involving simultaneous flow ofreactants and contact solids, the process comprising flowing com--mingled reactant vapors and solid contact material through a reactionzone, separating used contact material from reaction product vapors,subjecting contact material so separated to regeneration by controlledcombustion to remove burnable deposit therefrom, returning regeneratedcontact material at controlled and approximately reaction temperature tosaid reaction zone, and contacting flue gases resulting from saidcombustion with said mass before contacting the latter with saidreactants at controlled temperature to adjust the temperature of saidmass to reaction level.

2. In effecting hydrocarbon reactions in the presence of solid contactmasses, the process of simultaneously flowing hydrocarbon reactantvapors and preheated solid contact material through a reaction zone,feeding used contact solid separated from reaction products to a regeneration zone, therein removing burnable de- P posit from said solidby combustion, conveying regenerated solid issuing from saidregeneration zone while still in heated condition to said reaction zone,and adjusting the temperature of the regenerated mass to approximatelyreaction level before admitting the same to said reaction zone bypassing flue gases withdrawn from said regeneration zone while still hotfrom said combustion and at controlled temperature in heat exchangerelation therewith.

3. In effecting vapor phase hydrocarbon reactions in the presence ofsolid contact masses, the process comprising simultaneously flowingreactant vapors and solid adsorptive contact mass through a reactionchamber, separating said contact mass in substantially dry form fromhydrocarbon products, conducting said mass to a purging chamber separateand distinct from said reaction chamber and therein purging said mass ofreaction fluid, feeding the purged mass to a regeneration chamber andtherein subjecting it to combustion conditions to remove burnabledeposit therefrom, and utilizing a regulated quantity of fumes producedby said combustion to effect said purging.

4. In effecting hydrocarbon reactions involving simultaneous flow ofreactants and adsorptive contact solids, the process comprisingcommingling adsorptive solid heated to at least approximately reactiontemperature with reactant vapors, concurrently flowing a continuousstream of the commingled reactant vapors and adsorptive contact massthrough substantially the entire extent of a reaction zone, separatingcontaminated solid from the resulting products, feeding said solid to aregeneration zone, therein removing contaminating reaction products fromsaid solid by combustion, conveying the regenerated contact mass to saidreaction zone, utilizing spent regenerating medium to assist in themovement of the regenerated contact material, and controlling thetemperature of the regeneration fumes so utilized to adjust thetemperature of the mass during its conveyance to approximately reactionlevel.

5. In effecting hydrocarbon reactions involving simultaneous flow ofreactants and adsorptive contact solids, the process comprisingcommingling adsorptive solid heated to at least approximately reactiontemperature with reactant vapors, concurrently flowing a continuousstream of the commingled reactant vapors and adsorptive contact massthrough substantially the entire extent of a reaction zone, separatingcontaminated solid in dry form from the resulting reaction productvapors, feeding said solid to a regeneration zone, therein removingcontaminating reaction products from said solid by combustion, conveyingthe regenerated contact mass while still in heated condition to saidreaction zone, and utilizing hot spent regenerating medium to assist inthe movement of the regenerated contact material and to maintain thelatter at controlled temperature desired for its introduction into thereaction zone.

6. Ineffecting hydrocarbon reactions involving simultaneousflow ofreactants and an adsorptive contact solid through a reaction zone, theprocess comprising combining solid contact mass in heated condition withreactant vapors, flowing a continuous stream of the commingled vaporsand solid through the reaction zone, separating contaminated solid fromthe resulting products, feeding the separated solid to a regeneratingzone, therein removing burnable deposits from said solid by combustion,returning regenerated solid issuing from said combustion zone whilestill in heated condition into contact with said reactants, subjectingspent regenerating medium issuing from said regenerating zone topromoted combustion to remove active components therefrom, andcontacting fumes so treated and at controlled temperature with saidregenerated solid to condition the latter for contact with saidreactants.

7. In effecting hydrocarbon reactions involving simultaneous flow ofreactants and an adsorptive contact solid through a reaction zone, theprocess comprising combining solid contact mass in heated condition withreactant vapors, flowing a continuous stream of the commingled vaporsand solid through the reaction zone, separating contaminated solid indry form from the resulting reaction product vapors, feeding theseparated solid to a regenerating zone, therein removing burnabledeposits from said solid by combustion, returning regenerated solidissuing from said regeneration zone while still in heated condition intocontact with said reactants, subjecting spent regenerating mediumissuing from said regenerating zone to catalytic combustion to removeactive components therefrom, and utilizing the fumes resulting from saidcatalytic combustion to assist in conveying the regenerated contactmaterial back to said reaction zone.

8. In effecting vapor phase hydrocarbon reactions in the presence ofsolid contact masses,

1 the process comprising flowing commingled reactant vapors and solidadsorbent contact material through substantially the entire extent of areaction zone, separating said contact mass in dry form from theresulting reaction products by centrifugal action, burning combustibledeposits from said separated solid, pneumatically conveying burned solidwhile still hot from said burning back into contact with reactantvapors, and passing hot flue gases at controlled temperature issuingfrom said burning operation in heat exchange relation with said massprior to contacting the same with reactants to regulate the temperatureof the mass prior to said contacting step.

9. In apparatus for producing hydrocarbons, in combination, a vesselproviding a reaction chamber, means for supplying a stream of heatedreactant vapors commingled with heated contact mass to said chamber, aseparator adapted to separate solid from vapors, said separator beingprovided with an inlet connection, an overhead outlet for vapors, and abottom draw-oil for solid, means for purging spent contact mass ofadsorbed fluid, said purging means being provided with an inlet and anoutlet for purging chamber, means for supplying a stream of reactantvapors commingled with contact mass to a said chamber, a separator forseparating reaction products from contaminated contact materialconnected to said vessel, regenerating means arranged and adapted toreceive contaminated mass from said separator and to burn contaminatingdeposit from said mass, pneumatic conveying means arranged. and adaptedto conduct regenerated contact mass from said regenerating means towardsaid vessel, a conduit connection for conducting regeneration fumes fromsaid means to serve as pneumatic conveying medium in the latter, andmeans for effecting promoted combustion of said regenerated fumesdisposed in circuit between said regenerating means and. said conveyingmeans, thereby to remove burnable components from said fumes and provideconveying medium free of such contaminants.

11. In apparatus for producing hydrocarbons, in combination, a vesselproviding a reaction chamber, means for supplying a stream of heatedreactant vapors commingled with contact solid to said chamber, acentrifugal separator for separating reaction product vapors fromcontaminated contact material, said separator comprising inner and outercasings providing an inner chamber communicating with an outer chamberand an upper chamber, means disposed in said upper chamber formechanically inducing centrifugal action therein, an inlet connection tosaid inner chamber for admitting reaction product vapors and contactsolid thereto, an outlet connection in said outercasing disposed abovesaid last named means for discharging vapors from the separator, abottom draw-oil in said outer casing for discharging contact solidtherefrom, a conduit connecting said reaction chamber and said inletconnection, means for re-.

generating spent contact solid by controlled combustion provided withinlet and outlet connections for regenerating medium and regenerationfumes respectively, a conduit interconnecting said bottom draw-off andsaid regenerating means for conducting contact mass to the latter, meansfor pneumatically impelling contact solid, means for conductingregenerated contact material from said regenerating means to saidimpelling means, a, conduit for conducting regeneration fumes from saidlast named outlet connection to said impelling means to serve asimpelling medium therein, and a conduit interconnecting said impellingmeans and said first named means for conducting regenerated contactsolid to the latter.

12. A separator for separating hydrocarbon vapors from dry solid contactmaterial comprising an. outer casing provided with an overhead vaporline and a bottom draw-off for solid, an

